US4617035A - Gas adsorbent and process for producing same - Google Patents
Gas adsorbent and process for producing same Download PDFInfo
- Publication number
- US4617035A US4617035A US06/675,846 US67584684A US4617035A US 4617035 A US4617035 A US 4617035A US 67584684 A US67584684 A US 67584684A US 4617035 A US4617035 A US 4617035A
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- gas
- adsorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
Definitions
- This invention relates to a gas adsorbent including either a zeolitic adsorbent such as synthetic or natural zeolite or a silica-alumina adsorbent such as silica gel or alumina gel and also relates to a process for producing such a gas adsorbent.
- a gas adsorbent including either a zeolitic adsorbent such as synthetic or natural zeolite or a silica-alumina adsorbent such as silica gel or alumina gel and also relates to a process for producing such a gas adsorbent.
- Adsorbents in common use include synthetic and natural zeolites, activated carbon, and silica-alumina adsorbent which means silica gel, alumina gel or gel of their composite. These are employed singly as a mass or as a stack of multiple layers or a mixed bed of different adsorbents, depending on the intended use. Usually, individual adsorbents have limited applications; they do not singly serve all purposes but work only selectively and severally. Requirements of adsorbent performance for particular purposes are often not satisfied, and therefore various adsorbents possessing novel functions and capacities are needed.
- nitrogen oxides NO, NO 2 , etc.
- sulfur oxides SO x
- sulfur compounds H 2 S, organosulfur compounds, etc.
- adsorbents having optimum properties i.e., high adsorptivities
- Synthetic zeolites exhibit excellent performance in separating and drying hydrocarbons and in removing carbon dioxide gas, but the very low rates of nitrogen oxide removal by adsorption have hampered their practical use.
- silica gel and alumina gel are known adsorbents ror nitrogen oxide removal. However, their removal rates have again been too low for practical purposes.
- FIGS. 1 and 2 are graphs showing the results of comparative experiments on hydrogen sulfide-adsorbing capacities of activated carbon and a synthetic zeolite heat-treated in conformity with this invention.
- FIG. 3 is a graph showing the results of comparative experiments on carbonyl sulfide-adsorbing capacities of ordinary silica gel and one heat-treated under the invention.
- Samples I and II were taken as Samples I and the same zeolites heat-treated at 500° C. for 1 hour as Samples II. The latter looked blackish. About 80 g portions of Samples I and II were packed in cylindrical containers having an inside diameter of 23.9 mm and a length of 300 mm for uses as adsorption columns. Separately, a gaseous mixture of nitrogen with 10.3 ppm of nitrogen oxides was prepared in a high pressure vessel. The mixture was allowed to pass through the adsorption columns under identical conditions, and the nitrogen oxide content of the gas samples at the outlets of the columns was determined. Thus, the quantity of the gaseous mixture that had been flown through each column until the nitrogen oxide content of the test gas at the outlet reached 1 ppm was measured. The results are given in Table 1.
- the sizes of the pores opening on the surface of an adsorbent are at least 1000 ⁇ , or 0.1 ⁇ m, in the vicinities of their inlets, between 20 and 1000 ⁇ , or between 0.002 ⁇ m and 0.1 ⁇ m, midway, and between 4 to 20 ⁇ , or between 0.0004 to 0.002 ⁇ m, deep inside.
- These pores, classified by size, are called macropores, transitional pores, and micropores, respectively.
- the heat treatement in the mixture of carbon monoxide and hydrogen allowed the synthetic zeolites to have improved capacities of adsorbing and removing carbon dioxide gas from the test air.
- FIG. 2 shows the results.
- the breakthrough point of hydrogen sulfide in the heat-treated synthetic zeolite was found to be far behind that of activated carbon.
- silica-alumina adsorbents specific surface area: 150-700 m 2 /g
- Commercially available silica gel (specific surface area: 250-600 m 2 /g) was heat-treated in an atmosphere of a gaseous mixture consisting of 20% carbon monoxide, 10% carbon dioxide gas, and 70% nitrogen at 180° C. for 4 hours.
- COS carbonyl sulfide
- FIG. 3 represents the results.
- the breakthrough point of carbonyl sulfide in the heat-treated silica gel comes behind that in the untreated silica gel, thus suggesting better adsorptivity of the heat-treated silica gel.
- a synthetic zeolite or silica gel attains an improved efficiency of removing specified gases by adsorption upon heat treatment in carbon monoxide or its mixture with another gas such as hydrogen, carbon dioxide gas, nitrogen, or other inorganic gases.
- the heating temperature in the range from 100° to 700° C. has been found to give similar favorable results, though varying to minor degrees.
- Useful carbon-containing gases other than carbon monoxide which can yield similar satisfactory results are those that readily generate carbon by thermal decomposition, e.g., aromatic compounds such as benzene, toluene, and naphthalene; acyclic compounds (paraffinic, olefinic and acetylenic hydrocarbons) such as methane, ethane, propane, ethylene and alcohol; or their mixtures.
- aromatic compounds such as benzene, toluene, and naphthalene
- acyclic compounds paraffinic, olefinic and acetylenic hydrocarbons
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
TABLE 1 ______________________________________ Sample Sample Sample Kind of MS I II II/I ______________________________________ A (commercially available 25 l 660 l 26.4 "MS4A", pore size 4 Å) B (commercially available 6 l 100 l 16.7 "MS5A",pore size 5 Å) C (commercially available 6 l 84 l 14.0 "MS13X",pore size 10 Å) ______________________________________
CO→C+1/2O.sub.2
TABLE 2 ______________________________________ Sample Sample Sample Kind of MS I II II/I ______________________________________ A (commercially available 1.3 l 1.7 l 1.3 "MS4A", pore size 4 Å) B (commercially available 1.8 l 2.5 l 1.4 "MS5A",pore size 5 Å) C (commercially available 2.0 l 2.8 l 1.4 "MS13X",pore size 10 Å) ______________________________________
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US06/675,846 US4617035A (en) | 1984-11-28 | 1984-11-28 | Gas adsorbent and process for producing same |
Applications Claiming Priority (1)
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US06/675,846 US4617035A (en) | 1984-11-28 | 1984-11-28 | Gas adsorbent and process for producing same |
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US4617035A true US4617035A (en) | 1986-10-14 |
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US06/675,846 Expired - Fee Related US4617035A (en) | 1984-11-28 | 1984-11-28 | Gas adsorbent and process for producing same |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4931071A (en) * | 1989-03-09 | 1990-06-05 | The Boc Group, Inc. | Method for densely packing molecular sieve adsorbent beds in a PSA system |
US6451094B1 (en) | 1997-08-19 | 2002-09-17 | The Board Of Trustees Of The University Of Illinois | Apparatus and method for removal of vapor phase contaminants from a gas stream by in-situ activation of carbon-based sorbents |
US6461411B1 (en) | 2000-12-04 | 2002-10-08 | Matheson Tri-Gas | Method and materials for purifying hydride gases, inert gases, and non-reactive gases |
US6558454B1 (en) | 1997-08-19 | 2003-05-06 | Electric Power Research Institute, Inc. | Method for removal of vapor phase contaminants from a gas stream by in-situ activation of carbon-based sorbents |
US6695894B2 (en) | 2001-04-16 | 2004-02-24 | Electric Power Research Institute, Inc. | Method and apparatus for removing vapor phase contaminants from a flue gas stream |
US20040045437A1 (en) * | 2001-04-16 | 2004-03-11 | Ramsay Chang | Method and apparatus for removing vapor phase contaminants from a flue gas stream |
US6712878B2 (en) | 2001-01-18 | 2004-03-30 | Electric Power Research Institute, Inc. | Method and apparatus for renewable mercury sorption |
US20040097769A1 (en) * | 2002-11-14 | 2004-05-20 | Ou John D. Y. | Para-xylene production process employing in-situ catalyst selectivation |
US9604194B2 (en) | 2014-10-14 | 2017-03-28 | Saudi Arabian Oil Company | Synthesis of ordered microporous carbons by chemical vapor deposition |
Citations (14)
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US1917689A (en) * | 1929-09-25 | 1933-07-11 | United Verde Copper Company | Recovery of sulphur |
US2342856A (en) * | 1939-11-13 | 1944-02-29 | Standard Oil Dev Co | Regeneration of a contact catalyst |
US2501700A (en) * | 1943-09-03 | 1950-03-28 | Colorado Fuel & Iron Corp | Activated carbon manufacture |
US3151088A (en) * | 1960-12-02 | 1964-09-29 | Sinclair Research Inc | Catalyst demetallization |
US3168482A (en) * | 1960-08-05 | 1965-02-02 | Sinclair Research Inc | Process for the removal of nickel, iron, and vanadium from a silica based cracking catalyst |
BE769800A (en) * | 1971-04-23 | 1972-01-10 | Bergwerksverband Gmbh | MOLECULAR SIEVE CONTAINING CARBON AND SUITABLE TO SEPARATE SMALL MOLECULATED GASES FROM THE MIXTURES CONTAINING THEM |
DE2206982A1 (en) * | 1971-02-16 | 1972-08-24 | Nippon Denko Co. Ltd., Tokio | Insolubilization of chromate in chromium waste - to give harmless charcoal-bound product |
US3960771A (en) * | 1973-04-20 | 1976-06-01 | Japan Synthetic Rubber Co., Ltd. | Composite adsorbent |
US3960769A (en) * | 1971-04-23 | 1976-06-01 | Bergwerksverband Gmbh | Carbon-containing molecular sieves |
DE2458170A1 (en) * | 1974-12-09 | 1976-06-10 | Tanaka Giken Nagahama Kk | Gas deodoriser consisting of active carbon powder on activated clay - consists of material of controlled particle size and wt ratio of constituents |
US3979330A (en) * | 1971-04-23 | 1976-09-07 | Bergwerksverband Gmbh | Carbon containing molecular sieves |
JPS5393294A (en) * | 1977-01-26 | 1978-08-16 | Showa Denko Kk | Activation regeneration method of adsorbent used for the enrichment separation of hydrogen isotope |
JPS53119288A (en) * | 1977-03-29 | 1978-10-18 | Shintouhoku Kagaku Kougiyou Kk | Deodorant |
US4242104A (en) * | 1979-10-09 | 1980-12-30 | Union Carbide Corporation | Cyclic process for producing methane with catalyst regeneration |
-
1984
- 1984-11-28 US US06/675,846 patent/US4617035A/en not_active Expired - Fee Related
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1917689A (en) * | 1929-09-25 | 1933-07-11 | United Verde Copper Company | Recovery of sulphur |
US2342856A (en) * | 1939-11-13 | 1944-02-29 | Standard Oil Dev Co | Regeneration of a contact catalyst |
US2501700A (en) * | 1943-09-03 | 1950-03-28 | Colorado Fuel & Iron Corp | Activated carbon manufacture |
US3168482A (en) * | 1960-08-05 | 1965-02-02 | Sinclair Research Inc | Process for the removal of nickel, iron, and vanadium from a silica based cracking catalyst |
US3151088A (en) * | 1960-12-02 | 1964-09-29 | Sinclair Research Inc | Catalyst demetallization |
DE2206982A1 (en) * | 1971-02-16 | 1972-08-24 | Nippon Denko Co. Ltd., Tokio | Insolubilization of chromate in chromium waste - to give harmless charcoal-bound product |
BE769800A (en) * | 1971-04-23 | 1972-01-10 | Bergwerksverband Gmbh | MOLECULAR SIEVE CONTAINING CARBON AND SUITABLE TO SEPARATE SMALL MOLECULATED GASES FROM THE MIXTURES CONTAINING THEM |
US3960769A (en) * | 1971-04-23 | 1976-06-01 | Bergwerksverband Gmbh | Carbon-containing molecular sieves |
US3979330A (en) * | 1971-04-23 | 1976-09-07 | Bergwerksverband Gmbh | Carbon containing molecular sieves |
US3960771A (en) * | 1973-04-20 | 1976-06-01 | Japan Synthetic Rubber Co., Ltd. | Composite adsorbent |
DE2458170A1 (en) * | 1974-12-09 | 1976-06-10 | Tanaka Giken Nagahama Kk | Gas deodoriser consisting of active carbon powder on activated clay - consists of material of controlled particle size and wt ratio of constituents |
JPS5393294A (en) * | 1977-01-26 | 1978-08-16 | Showa Denko Kk | Activation regeneration method of adsorbent used for the enrichment separation of hydrogen isotope |
JPS53119288A (en) * | 1977-03-29 | 1978-10-18 | Shintouhoku Kagaku Kougiyou Kk | Deodorant |
US4242104A (en) * | 1979-10-09 | 1980-12-30 | Union Carbide Corporation | Cyclic process for producing methane with catalyst regeneration |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4931071A (en) * | 1989-03-09 | 1990-06-05 | The Boc Group, Inc. | Method for densely packing molecular sieve adsorbent beds in a PSA system |
US6451094B1 (en) | 1997-08-19 | 2002-09-17 | The Board Of Trustees Of The University Of Illinois | Apparatus and method for removal of vapor phase contaminants from a gas stream by in-situ activation of carbon-based sorbents |
US6558454B1 (en) | 1997-08-19 | 2003-05-06 | Electric Power Research Institute, Inc. | Method for removal of vapor phase contaminants from a gas stream by in-situ activation of carbon-based sorbents |
US6461411B1 (en) | 2000-12-04 | 2002-10-08 | Matheson Tri-Gas | Method and materials for purifying hydride gases, inert gases, and non-reactive gases |
US20030097932A1 (en) * | 2000-12-04 | 2003-05-29 | Tadaharu Watanabe | Method and materials for purifying hydride gases, inert gases, and non-reactive gases |
US7033418B2 (en) | 2000-12-04 | 2006-04-25 | Matheson Tri-Gas, Inc. | Method and materials for purifying hydride gases, inert gases, and non-reactive gases |
US6712878B2 (en) | 2001-01-18 | 2004-03-30 | Electric Power Research Institute, Inc. | Method and apparatus for renewable mercury sorption |
US20040045437A1 (en) * | 2001-04-16 | 2004-03-11 | Ramsay Chang | Method and apparatus for removing vapor phase contaminants from a flue gas stream |
US6905534B2 (en) | 2001-04-16 | 2005-06-14 | Electric Power Research Institute, Inc. | Method and apparatus for removing vapor phase contaminants from a flue gas stream |
US6695894B2 (en) | 2001-04-16 | 2004-02-24 | Electric Power Research Institute, Inc. | Method and apparatus for removing vapor phase contaminants from a flue gas stream |
US20040097769A1 (en) * | 2002-11-14 | 2004-05-20 | Ou John D. Y. | Para-xylene production process employing in-situ catalyst selectivation |
US20080033067A1 (en) * | 2002-11-14 | 2008-02-07 | Ou John D Y | Para-Xylene Production Process Employing In-Situ Catalyst Selectivation |
US7902414B2 (en) | 2002-11-14 | 2011-03-08 | Exxonmobil Chemical Patents Inc. | Para-xylene production process employing in-situ catalyst selectivation |
US9604194B2 (en) | 2014-10-14 | 2017-03-28 | Saudi Arabian Oil Company | Synthesis of ordered microporous carbons by chemical vapor deposition |
US10421058B2 (en) | 2014-10-14 | 2019-09-24 | Saudi Arabian Oil Company | Synthesis of ordered microporous activated carbons by chemical vapor deposition |
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Owner name: NIPPON SANSO KABUSHIKI KAISHA, 16-7, NISHISHINBASH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WAKAIZUMI, AKIRA;KAWAKAMI, HIROSHI;REEL/FRAME:004340/0423 Effective date: 19841109 Owner name: NIPPON SANSO KABUSHIKI KAISHA,JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WAKAIZUMI, AKIRA;KAWAKAMI, HIROSHI;REEL/FRAME:004340/0423 Effective date: 19841109 |
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